2-(4-Hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxane-6-aldehyde 8,the key intermediate of sinaiticin 10,was synthesized in 6 step from caffeic acid 4 and 4- hydroxybenzsaldehyde 1.the coupling reaction is the key step.
A library of new 1,4-benzodioxane-6-carboxylic acid amide analogs was designed and synthesized. These analogs were obtained in six steps from gallic acid. Firstly, esterification of the commercially available gallic a...A library of new 1,4-benzodioxane-6-carboxylic acid amide analogs was designed and synthesized. These analogs were obtained in six steps from gallic acid. Firstly, esterification of the commercially available gallic acid in methanol in the presence of sulfuric acid afforded methyl 3,4,5-trihydroxybenzoate (9) in satisfactory yield. The ester 9 was then reacted with an excess of 1,2-dibromoethane in the presence of K<sub>2</sub>CO<sub>3</sub> in acetone to furnish the 6,8-disubstituted-1,4-benzodioxane (10) in 45% yield. The reaction of 10 with various mercaptans gave the sulfide derivative 11, 12, and 13 in moderate yield. Subsequent hydrolysis of the methyl ester in 13 followed by conversion to the acid chloride and reaction of the acid chloride intermediate with different commercially available primary and secondary amines gave the amide analogs 18 - 32 with an average yield of 43%. Conversion of the sulfide group in Compound 23 to Sulfoxide 33 or Sulfone 34 was accomplished by reaction with either 30% H<sub>2</sub>O<sub>2</sub>/TeO<sub>2</sub> or 30% H<sub>2</sub>O<sub>2</sub>, respectively. The structures of the synthesized compounds were characterized using FTIR, <sup>1</sup>H-NMR, <sup>13</sup>C-NMR, and high-resolution ESI-MS.展开更多
An enantioselective and regioselective total synthesis approach to chiral 1,4-benzodioxane lignans(2R,3R)- and (2S,3S)-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde was reported firstly.
以3,4-二羟基苯丙烯酸（咖啡酸）为原料,经酯化和仿生氧化偶联反应得到苯并呋喃类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰基-5-甲氧羰基乙烯基-7-羟基-2,3-二氢苯并呋喃（1）和苯并二氧六环类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰...以3,4-二羟基苯丙烯酸（咖啡酸）为原料,经酯化和仿生氧化偶联反应得到苯并呋喃类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰基-5-甲氧羰基乙烯基-7-羟基-2,3-二氢苯并呋喃（1）和苯并二氧六环类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰基-6-甲氧羰基乙烯基-2,3-二氢-1,4-苯并二氧六环（2）,然后经乙酰化、DDQ氧化脱氢、Pd/C 催化氢化、氢化铝锂还原、碱性条件下脱乙酰基等反应,合成了一系列苯并呋喃新木脂素类化合物3~7和苯并二氧六环新木脂素类化合物8~10.所合成化合物的结构已由核磁共振法（1 H NMR,13 C NMR）、质谱法（MS）进行了表征.其中5~7,9和10是未见文献报道的新化合物,8为天然产物异美商陆醇A.采用MTT法对所合成的苯并呋喃新木脂素类化合物1,3~5进行了生物活性测试.结果表明：化合物1,3,4和5对白血病细胞（HL-60）、肺癌细胞（A-549）、乳腺癌细胞（MCF-7）、结肠癌细胞（SW-480）、肝癌细胞（SMMC-7721）有良好的体外生长抑制活性.展开更多
A number of benzodioxane compounds were synthesized using the pal1adium-catalyzedetherification of aryl halides by employing triphenylphosphan ligand. This method was used askey step in the synthesis of isoamericanol ...A number of benzodioxane compounds were synthesized using the pal1adium-catalyzedetherification of aryl halides by employing triphenylphosphan ligand. This method was used askey step in the synthesis of isoamericanol A and isoamericanin A.展开更多
文摘2-(4-Hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxane-6-aldehyde 8,the key intermediate of sinaiticin 10,was synthesized in 6 step from caffeic acid 4 and 4- hydroxybenzsaldehyde 1.the coupling reaction is the key step.
文摘A library of new 1,4-benzodioxane-6-carboxylic acid amide analogs was designed and synthesized. These analogs were obtained in six steps from gallic acid. Firstly, esterification of the commercially available gallic acid in methanol in the presence of sulfuric acid afforded methyl 3,4,5-trihydroxybenzoate (9) in satisfactory yield. The ester 9 was then reacted with an excess of 1,2-dibromoethane in the presence of K<sub>2</sub>CO<sub>3</sub> in acetone to furnish the 6,8-disubstituted-1,4-benzodioxane (10) in 45% yield. The reaction of 10 with various mercaptans gave the sulfide derivative 11, 12, and 13 in moderate yield. Subsequent hydrolysis of the methyl ester in 13 followed by conversion to the acid chloride and reaction of the acid chloride intermediate with different commercially available primary and secondary amines gave the amide analogs 18 - 32 with an average yield of 43%. Conversion of the sulfide group in Compound 23 to Sulfoxide 33 or Sulfone 34 was accomplished by reaction with either 30% H<sub>2</sub>O<sub>2</sub>/TeO<sub>2</sub> or 30% H<sub>2</sub>O<sub>2</sub>, respectively. The structures of the synthesized compounds were characterized using FTIR, <sup>1</sup>H-NMR, <sup>13</sup>C-NMR, and high-resolution ESI-MS.
文摘An enantioselective and regioselective total synthesis approach to chiral 1,4-benzodioxane lignans(2R,3R)- and (2S,3S)-2-(4-hydroxy-3-methoxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde was reported firstly.
文摘以3,4-二羟基苯丙烯酸（咖啡酸）为原料,经酯化和仿生氧化偶联反应得到苯并呋喃类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰基-5-甲氧羰基乙烯基-7-羟基-2,3-二氢苯并呋喃（1）和苯并二氧六环类化合物2-（3′,4′-二羟基苯基）-3-甲氧羰基-6-甲氧羰基乙烯基-2,3-二氢-1,4-苯并二氧六环（2）,然后经乙酰化、DDQ氧化脱氢、Pd/C 催化氢化、氢化铝锂还原、碱性条件下脱乙酰基等反应,合成了一系列苯并呋喃新木脂素类化合物3~7和苯并二氧六环新木脂素类化合物8~10.所合成化合物的结构已由核磁共振法（1 H NMR,13 C NMR）、质谱法（MS）进行了表征.其中5~7,9和10是未见文献报道的新化合物,8为天然产物异美商陆醇A.采用MTT法对所合成的苯并呋喃新木脂素类化合物1,3~5进行了生物活性测试.结果表明：化合物1,3,4和5对白血病细胞（HL-60）、肺癌细胞（A-549）、乳腺癌细胞（MCF-7）、结肠癌细胞（SW-480）、肝癌细胞（SMMC-7721）有良好的体外生长抑制活性.
文摘A number of benzodioxane compounds were synthesized using the pal1adium-catalyzedetherification of aryl halides by employing triphenylphosphan ligand. This method was used askey step in the synthesis of isoamericanol A and isoamericanin A.
